Reactive dyestuffs

ABSTRACT

Dyestuffs of the formula:   WHEREIN Z represents an acyl or heterocycylc radical containing at least one cellulose-reactive substituent, n is 0 or 1 and Dm is a N,N&#39;&#39;-diamine residue. These dyes are cellulose-reactive dyes giving bright reddishblue shades of high tinctorial value and having good fastness to washing and to light.

United States Patent Parton REACTIVE DYESTUFFS [75] Inventor: BrianParton, Manchester, England 21 Appl. No.: 389,546

[30] Foreign Application Priority Data Sept. 6, 1972 United Kingdom41351/72 [52] US. Cl. 260/246 R; 8/1 B; 8/54.2;

[51] Int. Cl C09b 19/02 [58] Field of Search 260/246 [56] ReferencesCited UNITED STATES PATENTS 2,086,871 7/1937 Kranzlein et a1 260/246FOREIGN PATENTS OR APPLICATIONS 192,053 10/1937 Switzerland 260/246195,862 5/1938 Switzerland 260/246 Primary Examiner-Harry I. MoatzAttorney, Agent, or FirmCushman, Darby & Cushman July 1, 1975 wherein Zrepresents an acyl or heterocycylc radical containing at least onecellulose-reactive substituent, n is 0 or 1 and Dm is a N,N'-diamineresidue.

These dyes are cellulose-reactive dyes giving bright reddish-blue shadesof high tinctorial value and having good fastness to washing and tolight.

5 Claims, No Drawings REACTIVE DYESTUFFS This invention relates to newreactive dyestuffs and provides dyestuffs of the formula:

2 3-(4 :5-dichloro-pyridaz-6-on-l -yl)benzoyl,5-chloro-2-methylsulphonyl-6-methyl-pyrid-4-yl,2,4-difluoro-S-chloropyrimid-6-yl, and more particularly s-triazin-2-yland pyrimidin-Z-yl wherein Z represents an acyl or heterocyclic radicalcontaining at least one cellulose-reactive substituent, n is 0 or I andDm is a N,N'-diamine residue.

The symbol Dm may represent, for example, the residue of an aliphatic,aromatic or heterocyclic diamine, e.g. alkylene or naphthylene diaminesor piperazine, but more especially a diamine of the benzene series whichcontains one or two benzene rings, c.g. a phenylene, sulphophenylene,disulphophenylene, disulphodiphenylene, disulphostilbene,disulphodiphenylmethane, disulphodiphenylamine, disulphodiphenylurea, ordisulphodiphenoxyethane diamine residue.

By "cellulose-reactive substituent" is meant an unsaturated linkage or asubstituent capable of reacting with the hydroxyl groups of thecellulose molecule in the presence of an alkaline substance andattaching the dyestuff molecule by a covalent linkage.

As examples of groups represented by Z, there may be mentionedafi-unsaturated acyl radicals of aliphatic carboxylic acids, forexample, acrylic acid, a-chloroacrylic acid, propiolic acid, maleic acidand monoand di-chloromaleic acids; also the acyl radicals of acids whichcontain a substituent which reacts with cellulose in the presence of analkali, e.g. the radical of a halogenated aliphatic acid such aschloroacetic acid, ,B-chloroand ,B-bromo-propionic acids anda,,8-dichloroand dibromo-propionic acids. Other examples ofcellulosereactive groups are tetrafluorocyclobutyl carbonyl,trifluorocyclobutenyl carbonyl, tetrafluorocyclobutylethenyl carbonyl,trifluorocyclobutenylethenyl carbonyl, and heterocyclic radicals whichcontain 2 or 3 nitrogen atoms in the heterocyclic ring and at least onecellulose-reactive substituent on a carbon atom of the ring.

As examples of such heterocyclic radicals, there may be mentioned, forexample:

2:3-dichloro-quinoxaline-5- or -6-carbonyl.

2:4-dichloro-quinazoline-6-carbonyl, l:4-dichloro-phthalazine--carbonyl,4:5-dichloro-pyridazonl -yl,

2:4-dichloro-pyrimidine-5-carbonyl,

wherein Y represents a group of atoms necessary to form a 5- or6-membered heterocyclic ring which may carry substituents or form partof a fused'ring system: or a quaternary ammonium or pyridinium group; ora group of the formula: I

wherein R and R each represents the same or different alkyl, cycloalkyl,aryl or aralkyl group. or R and R together form, together with thenitrogen atom, a 5- or 6-membered heterocyclic ring: or a group of theformula:

wherein R and R may be the same or different and each represents ahydrogen atom or an alkyl, aryl or aralkyl group.

In the cases where the pyrimidine ring or triazine ring carries only onesuch reactive substituent, the said ring may have a non-reactivesubstituent on the remaining carbon atoms. 7

By a non-reactive substituent there is meant a group which is bound by acovalent bond to a carbon atom of the triazine or pyrimidine nucleus,which covalent bond is not ruptured under the conditions used forapplication of the reactive dye.

As examples of such substituents, there may be mentioned, for example,primary amino and hydroxyl groups, also monoor disubstituted aminogroups, etherified hydroxyl and etherified mercapto groups; in the caseof substituted amino groups, this class includes, for example, monoanddi-alkylamino groups in which the alkyl groups preferably contain atmost 4 carbon atoms, and which may also contain substituents forexample, hydroxyl or alkoxy groups, and phenylamino and naphthylaminogroups preferably containing sulphonic acid substituents; in the case ofetherified hydroxyl and mercapto groups, this class includes, forexample, alkoxy and alkylthio groups preferably those of low molecularweight, i.e. having up to 4 carbon atoms and phenoxy, phenylthio,naphthoxy or naphthylthio groups; as particular examples of all theseclasses there may be mentioned, for example. methylamino, ethylamino,dimethylamino, B-hydroxyethylamino, di-(B-hydroxyethyl)amino,B-chloroethylamino, cyclohexylamino, anilino, sulphophenylamino,disulphophenylamino, N-

methylsulphophenylamino, N B-hyd'roxyethylsulphophenylamino, mono-,diand tri-sulphonaphthylamino, sulpho-o-tolylamino, carboxyphenylaminoand sulphocarboxyphenylamino, N-wsulphomethylphenylamino, methoxy,ethoxy, and butoxy, phenoxy, methylphenoxy. chlorophenoxy and phenylthiogroups. Chlorine atoms or cyano, nitro, carboxy and carbalkoxy groups inthe 5-position of a pyrimidyl radical come into the category ofnonreactive substituents.

The invention also provides a process for manufacture of the newdyestuffs which comprises reacting a compound of the formula:

with the acid chloride of a carboxylic or sulphonic acid which containsa cellulose-reactive substituent or a heterocyclic compound whichcontains a halogen atom and at least one cellulose-reactive substituentattached to carbon atoms of the ring. i.e. a compound of the formulaZ.Cl (6), when n in formula (l) 0. I

The above process can conveniently be carried out by stirring thereactants in an aqueous medium. optionally in the presence of awater-soluble organic solvent. at a temperature within the range 0l()0C.and preferably maintained at a pH of from 5-8.

4 As examples o f'compounds of formula (6) which may be used, there maybe mentioned, for example, acid halides of oz, ,B-unsaturated aliphaticacids such as chloromaleic anhydride,

propiolyl chloride.

acryloyl chloride,

the acid chlorides of halogenated aliphatic acids such as chloroacetylchloride,

sulphochloroacetyl chloride,

B-bromoand B-chloro-propionyl chloride,

azB-dichloroand dibromo-propionyl chlorides,

2,2,3,3-tetrafluorocyclobutyl carbonyl chloride,

B-( 2,2,3,3-tetrafluorocyclobutyl)acryloyl chloride,

2,3,3-trifluorocyclobut-l-enyl carbonyl chloride,

[3-( 2,3 ,3-trifluorocyclobut- 1-enyl)acryloyl chloride, andheterocyclic compounds which contain at least 2 nitrogen atoms in theheterocyclic rings and which contain two or more halogen, especiallychlorine atoms in the ortho positions to the nitrogen atoms, such as2:3-dichloro-quinoxaline-5- and -6-carbonyl chlorides, I2:4-dichloro-quinazoline-6-carbonyl chloride,

l :4-dichloro-phthalazin-6-carbonyl chloride,

2:4-dichloro-pyrimidine-5earbonyl chloride,

/3-( 4:5-dichloro-pyridazonyll )propionyl chloride,

l-('4-chlorocarbonylphenyl )-4:5-dichlo ro-6 pyridazone,

2:4:6-tribrornoand trichloro-pyrimidines,

2:4.5:o-tetrachloropyrimidine,

5-methyl-2z4z6-trichloropyrimidine, 5-nitro.-2:4:-trichloropyrimidine,2:4-dichloro-5'-nitro-6-methyl-pyrimidine, 2:4-dichloro5-nitropyriinidine,

2:4:6-trichloro-5-cyanopyrimidine, v

5-ethoxycarbonyl-2z l-dichloro-pyrimidine,

2:4-dichloropyrimidin'e-5-carbonyl chloride,

4,5-dichloro-2-methylsu'lphonyl-6-methylpyrimidine,

2,4,6-trifluoro-S-chloropyrimidine,

cyanuric bromide, l v cyanuric chloride; the primary condensationproducts of cyanuric bromide or cyanuric chloride with ammonia, analkali metal sulphite or thiocyanate or an organic mercaptan, hydroixycompound or an organic primary oi secondary amine, for example:'

methanol, l

ethanol.

iso-propanol, phenol,

o-, mand p-chlorophenols,

0-. mand p-cresols,

0-, m and p-sulphophenols,

thiophenol,

thioglycollic acid,

dimethyldithiocarbamic acid,

mercaptobenzthiazole, I

thioacetamide,

methyl-.

dimethyl-,

ethyl-,

diethyl-,

n-propyl-.

iso-propyl-,

butyl-.

hexyland cyclohexylamines.

toluidines,

i also the secondary condensation products of cyanuric chloride withalkali metal sulphites, alkali metal thiocyanates, phenols andthiophenols containing an electronegative substituent, and compounds ofthe formulae:

\1 i i.'S-t. Y n-s-C-N,

and m? wherein Y, R, R*, R and R have the meanings stated above,

For manufacture of the dyes of formula (I) in which n l by this process,there is usedaheterocyclic compound of the formula: I

wherein the symbols Dm and Z have the meanings stated earlier, and whichitself can be obtained by reacting a diamine with 1 mole of cyanuricchloride and one mole of a compound of the formula Z.Cl as illustratedabove.

As examples of diamines which may be used in this connection there maybe mentioned heterocyclic diamines, e.g. piperazine, aliphatic diaminese.g. alkylene-, hydroxyalkyleneor sulphatoalkylene-diamines, cg.

ethylene diamine,

propylene diamine,

1,3-diaminopr0pz 1ne.

,B-hydroxyethylaminoethylaminc,

Z-hydroxy-l ,3-diaminopropane,

2-sulphat0-1.3-diaminopropane.

naphthylene diamine sulphonic acids, e.g.

2,6-diaminonaphthalene-l,5- and 4,8-disulphonic acids,

l,5diaminonaphthalene-3,7-disulphonic acid and diamine derivatives ofmonoand di-cyclic compounds of the benzene series, e.g. m-andp-phenylenediamines,

1,3-phenylenediamine-4-sulphonic and 4,6-

disulphonic acids, l,4-phenylenediamine-Z-sulphonic and 2,5-

disulphonic acids, 4,4'-diaminostilbene-2,2'-disulphonic acid,benzidine-2,2-disulphonic acid 3,3- and 4,4-diaminodiphenylureas4,4'-diaminodiphenylurea-2,2- and 3,3'-disulphonic acids,

4,4-diaminodiphenylmethane,

4,4f-diaminodiphenoxyethane-Z,2-disulphonic acid 4,4'-diamin0diphenylsulphone 4-methylaminoaniline-2-sulphonic acid.

The compounds of formula (5) used in the above process can be obtainedby reacting 2,3,5,6-tetrachlorobenzoquinone with two moles of 2,6-diaminonaphthalene-4,8-disulphonic acid and heating the condensationproduct in oleum to effect ring closure.

The resulting product has a nitrogenzsulphur ratio of 4:3 and isbelieved to-be the indicated compound, possibly admixed with smallamounts of diand tetrasulphonic acid derivatives.

The dyes of formula 1 in which n has the value I can also be obtained byreacting two moles of a diamine, as illustrated above, in either orderwith two moles of a compound of the formula Z.Cl, as illustrated above,and with one mole of the new dyestuff of the formula:

The dyes of formula (1) in which Z represents a striazine nucleussubstituted by a chlorine or bromine atom and an amino or substitutedamino group can also be obtained by reacting the corresponding dyestuffin which Z represents the dichloroor dibromo-s-triazine group withammonia or an amine.

This process can conveniently be carried out by stirring the reactantsin an aqueous medium, optionally in the presence of a water-solubleorganic solvent, at a temperature of from 3060C, and preferably maintaining the pH at from 5-8 by adding an acidbinding agent to neutralisethe hydrogen halide formed during the reaction. Suitable acid-bindingagents are alkali metal hydroxides, carbonates and bicarbonates, or anexcess of ammonia or aliphatic amine where this is one of the reactants.

As amines, there can be used. for examplefany'of those enumerated in theabove paragraph.

The cellulose-reactive dyes of formula (I) wherein thecellulose-reactive group is a s-triazine nucleus substituted by SO H, aquaternary ammonium group or a group of formulae (2), (3) and (4), canbe obtained in a similar manner by reacting a cellulos-reactive dye offormula l containing a striazine group substituted by at least onechlorine or bromine atom withan alkali metal salt of sulphurous acid, atertiary amine or a compound of formulae (7), (8) and (9).

The new dyestuffs can be used for colouring a variety of materials, e.g.natural and synthetic polyamide materials, e.g. wool and nylon, butmoreparticularly natural or artificial cellulose materials, eg. cotton.linen and viscose rayon, which then dye or print in the presence ofalkali to give bright reddish blue shades of high tinctorial valuehaving good fastness to lightarid washing treatments.

The invention is illustrated by the following Examples in which partsand percentages are by weight.

EXAMPLE I described below, are dissolved in 800 parts of water and thesolution is added to a suspension of.3.20 parts of cyanuric chloride ina mixture of 40 parts of acetone and 100 parts of water at 5C. The pH ismaintained at 5.5-6.5 throughout and stirring is continued under theseconditions for 3% hours. The resultant solution is filtered and theproduct is precipitated from the filtrate by the addition of sodiumchloride (250 g/l). The dyestuff is filtered off and dried at roomtemperature. It dyes cellulose textile materials in bright reddish-blueshades.

The 3,12-diamino-8,l7-dichlorodibenzo[c,n]- triphendioxa'zine used inthe above Example was obtained follows:-

690 Parts of the disodium salt of 2.6-diaminonaphthalene-4,8-disulphonic acid are dissolved in 3000 parts ofwater and an ethanolic slurry of 246 parts of2.3.5,6-tetrachlorol,4-benzoquinone is added. The mixture is stirred at60C for 2 hours, the pH being maintained at 6-7 throughout by theaddition of 2N sodium hydroxide solution. 600 parts of sodium chlorideare added to the cooled solution and the product is filtered off andwashed with 20% brine and then dried at 80C to give a brown solid.

3, l 2-diamino-8. l 7-:

A mixture of 40 parts of the solid and 400 parts of 26% oleum is stirredat 95C for hours, then added to 8000 parts of ice-water. The precipitateis filtered off, washed with saturated potassium chloride solution anddried at 80C. It is purified as follows:

28.5 Parts of the crude cyclisation product are stirred with 6000 partsof water, and l00 parts of saturated potassium acetate solution added.The resultant solution is filtered. and the filtrates treated with afurther 3000 parts of saturated potassium acetate solution. Theprecipitate is filtered off, washed with 30% potassium acetate solution,then ethanol and finally dried at 80C to give a crystalline red solidwhich dissolves in water to give a bright blue solution. 8

On subjecting the purified product to elemental analysis the N25 ratioweight is 4.7:8.5, corresponding to an atomic ratio of 4:3.1.

- Dyestuffs ofa similar shade are obtained if the cyanuric chloride usedin Example 1 is replaced by an equivalent amount of any of thefollowing:

2 2.4-dichloro-6-methoxy-s-triazinc 3 2,4-dichloro-fi-n-hutoxy-striazine4 2,4-dichloro-o-phcnoxy-s-triazine 5 2.4dichloro-6-aniIino-s-triazine 62.4-dichloro6-B-ethoxyethoxy-s-triazine 72.4-dich|oro-6-methylamino-s-triazine 8 2.4-dichloro-o-amino-s-triazine9 2.4-dichloro-tvdimethylamino-s-triazine l0 Z.4,6-trichloropyrimidine l1 2.4.5.6-tetrachloropyrimidinc l2 2,4-dichloropyrimidine-5-carbonylchloride 13 2.4.6-trichloro-5-cyanopyrimidine l4 2.4-dichloro-6-B-hydroxyethylamino-s-triazine l5 2.4.6-trifluoro-5-chloropyrimidine l 62,4-dichloro-6-4'-sulphophenoxy-s-triazine l 72,4-dichloro-6-4'chlorophenoxy-s-triazine l8 2,4-dichloro-63'-sulphophenoxy-s-triazine l9 2 .4-dichloro-6-phenylthio-s-triazine2.4-dichloro-6-B-sulphatoethylamino-s-triazine 2l 2,4-dichloro-6-(m-B-sulphatoethylsulphonylanilino) -s-triazine 222.4-dichloro-6-cyclohexylamino-s-triazine 232.4-dichloroquinazoline-6-sulphonyl chloride 242.4-dichloroquinazoline-6-carbonyl chloride 252.3-dichloroquinoxalineXw-carbonyl chloride 26 B-(4.S-dichloropyridaz-o-onl -yl )propionyl chloride 72.4.6-tribromopyrimidine 282-methylsulphonyl-4.5-dichl0r0-6-methylpyrimidine 293.6-dichloropyridazine-4-carbonyl chloride 302.3-dichloroquinoxaline-(m-sulphony] chloride 3 ll,4-dichlorophthalazine-o-carbonyl chloride 32 B-(2.2;3.3-tetrafluorocyclohutyl)acryloyl chloride2.2.3;3-tctrafluorocyclobutyl carbonyl chloride5-chloro-6-methyl-Z.4bis( methylsulphonyl )pyrimidine 35 6-n1ethvl-2.4-bis(mcthylsulphonyl)pyrimidine2.4-dichlor0-6-B-methoxyethoxy-s-triazinc EXAMPLE 37 A neutral solutionof 3.8 parts of metanilic acid in 100 parts of water is added to asuspension of 4.4 parts of cyanuric chloride in a mixture of 40 parts ofacetone and 160 parts of water at 05C. The pH is maintained at 5.5-6.5throughout by addition of 2N sodium hydroxide and stirring is continuedunder these conditions for 1 hour. The solution is screened and l 1.0parts of the 3.l2 diamino-8,l7-dichlorodibenzlc,nl-triphendioxazinecontaining 3.0 potassium sulphonate groups per molecule purified asdescribed in Example 1 is added. After stirring at pH 5.5-6.5 and C for10 hours the reaction mixture is cooled to 20C and potassium chloride(300 g/l) added. The precipitate is filtered off, washed with saturatedpotassium chloride solution then dried at room temperature. The dyestuffobtained dyes cellulosic textile materials in bright reddish-blueshades.

Dyestuffs giving a similar shade are obtained if the metanilic acid usedin the above Example is replaced by an equivalent of any of thefollowing:

EXAMPLE 56 A solution of 4.5 parts of l,4-phenylenediamine-2,5-disulphonic acid in 70 parts of water is added to a suspension of 6.4parts of cyanuric chloride in 200 parts of water and 35 parts ofacetone, and the mixture is stirred at O5C, pH 6-7 for 10 hours.

The resulting solution is then added to a solution of 10 parts of3,l2-diamino-8,l7-dichlorodibenzotriphenodioxazine trisulphonic acid in800 parts of water and the mixture is stirred at 45C, pH 67 for 5 hours.The product is isolated by salting and drying. lt dyes cellulose textilematerials in bright reddish-blue shades.

Similar products are obtained if the 1,4- phenylenediamine used in theabove example is replaced by an equivalent amount of;-

Example 57 l,3'phenylenediamine-4-sulphonic acid 58l.4-phe11ylenediamine-Z-sulphonic acid 59 l3-phenylenediamine-4;6-disulphonic acid Other similar dyestuffs areobtained if the diamine of column ll of the following table is reactedwith 1 mole of the reaction product of cyanuric chloride and thecompound of column lll, and then with 1 mole of cyanuric chloride, andthe resulting product used in place of the solution of paragraph one ofExample 56:

-Continued Ex. ll lll 4,6-disulphonic acid phenol 7 l vfi-hydroxycthylamine 72 ethylene diamine 2,5-disulphoaniline 73 'f2-carboxy-4-sulphoaniline 74 I l-naphthylaminc-3,6,8-

trisulphonie acid 75 2sulphato-L3- 2-chloro-4-sulphoanilinediaminopropane 76 Z-methyl-S-sulphoaniline 77 2-naphthylamine-4.8

disulphonic acid EXAMPLE 78 3.2 parts of cyanuric chloride are reactedwith 10 parts of 3,12-diar nino-8, l7-dichlorodibenzotriphendioxazinetrisulphonic' acid as described in Example 1. Instead of isolating theproduct, a'solution obtained by condensing 3.2 parts of cyanuricchloride with 3.2 parts of l,3-phenylenediam inersulphonic acid and 3.]parts of metanilic acid in 300 parts of water is added and the mixtureis stirred at 50C,pH 6-7 for- 10 hours;

The product is isolated by salting;-it is identical with Example 60.Examples 57, 58, 61 to 65 and 72 to 77 can also be made in an analogousmanner.- 7

EXAMPLE 79 3.2 parts of cyanuric chloride arefreacted .with 10 parts of3,l2-diamino-8,l 7-dichlorodibenzotriphendioxazine trisulphonic acid asdescribed in Example 1. Instead of isolating the product. a solution of3.2 parts of l,3-phenylenediamine-4-sulphonic acid in 300 parts of wateris added and the mixture is stirred at 45C, pH 4-4.5 for 6 hours.

A solution obtained by reacting 3.2 parts of cyanuric chloride with 3.1parts of metanilic acid at 0-5C, pH 6.5 for 2 hours in 200 parts ofwater is added and the mixture is stirred at 4550C, pH 6-7 for 8 hours.

The product is isolated by salting and isan isomer of Example 60.Examples 56 and 59, and isomers of Examples 57, 58, 61 to 65 and 72 to77 can be made in an analogous manner.

EXAMPLE 80 9.2 parts of 3,l2-bis(dichloro-s-triazinylamino)-8. l 7-dichlorodibenzlc,n-triphendioxazine having 3.0 potassium sulphonatesubstituents per molecule. obtained as described in Example 1, arestirred at 25C for 5 hours with 1.5 parts of concentrated ammoniumhydroxide liquor (S.G. 0.88) and 800 parts of water. The product isprecipitated by the addition of salt and collected by filtration. It isidentical with Example 8 and dyes cellulosic textile materials in brightreddish-blue shades.

Other dyestuffs described in the earlier Examples can be obtained bysubstituting the appropriate amine for the ammonium hydroxide usedabove. Thus the use of aniline, methylamine, dimethylamine orethanolamine gives Examples 5, 7, 9 or 14 respectively. Examples 20-22and 37-55 can be obtained in an analogous manner. Similarly, Examples60. 62-65, 67-69 and 71-77 can be obtained by reacting the products ofExamples 5659, with ammonia or the appropriate amine.

I claim: i

l. A dyestuff of the formula 13 14 2. A dyestuff as claimed in claim 1having the for- 4. A dyestuff as claimed in claim 1 having the formula:mula:

H038 Cl W/ \w/Cl N\ O N cl Y x o 01 N N l Cl SOBH C]. N J NH 3 3. Adyestuff as claimed in claim 1 having the for- 5. A dyestuff as claimedin claim 1 having the formula: mula:

H0 5 Cl NHI YTH s0 01 /O l 7 l l N 01 so n W 5035 i k i NH N NH S0 11 1so H NH $0 K 01 5 01

1. A DYESTUFF OF THE FORMULA
 2. A dyestuff as claimed in claim 1 havingthe formula:
 2. 4,5,6-trichloropyrimid-2-yl,
 3. 2,4-dichloropyrimid-5-ylcarbonyl,
 3. A dyestuff as claimed in claim 1 having the formula:
 4. Adyestuff as claimed in claim 1 having the formula: 4.4,6-dichloro-5-cyanopyrimid-2-yl,
 5. 4,6-difluoro-5-chloropyrimid-2-yl,5. A dyestuff as claimed in claim 1 having the formula: 6.2,4-dichloroquinazolin-6-ylsulphonyl,
 7. 2,4-dichloroquinazolin-6-ylcarbonyl,
 8. 2,3-dichloroquinoxalin-6-ylcarbonyl,
 9. Beta-(4,5dichloropyridaz6-on-1-yl) propionyl, 9.B-(4,5DICHLOROPYRIDAZ6-ON-1-YL) PROPIONYL,
 10. 4,6-DIBROMOPYRIMID-2 YL,11. 2-METHYLSULPHONYL-5-CHLORO-6-METHYLPYRIMID-4-YL, 12.3,6-DICHLOROPYRIDAZIN-4-YLCARBONYL, 13.2,3-DICHLOROQUINOXALIN-6-YLSULPHONYL, 14.1,4-DICHLOROPHTHALAZIN-6-YLCARBONYL,
 10. 4,6-dibromopyrimid-2-yl, 11.2-methylsulphonyl-5-chloro-6-methylpyrimid-4-yl, 12.3,6-dichloropyridazin-4-ylcarbonyl, 13.2,3-dichloroquinoxalin-6-ylsulphonyl, 14.1,4-dichlorophthalazin-6-ylcarbonyl,
 15. Beta-(2,2,3,3-tetrafluorocyclobutyl) acryloyl, 15.B-(2,2,3,3-TETRAFLUOROCYCLOBUTYL) ACRYLOYL, 16.2,2,3,3-TETRAFLUOROCYCLOBUTYLCARBONYL, 17.2,METHYLSULPHONYL-6-METHYLPYRIMID-4-YL AND 16.2,2,3,3-tetrafluorocyclobutylcarbonyl, 17.2,methylsulphonyl-6-methylpyrimid-4-yl and